Disazo-dyestuffs and process of making same



Patented Mar. 15, 1932 UNITED STATES ATENT OFFICE JOSEPH G-YR, OF BASEL, SWITZERLAND, .ASSIGNOR TO THE FIRM OF SOCIETY 0]! CHEMICAL INDUSTRY IN BASLE, 0F BASEL, SWITZERLAND DISAZO -DYESTUFFS AND PROCESS OF MAKING SAME No Drawing. Application filed January 28, 1930, Serial No. 424,021, and in Switzerland February 2, 1929.

The present invention relates to the manufacture of new disazo-dyestuffs which are particularly suitable for the production of fast and level blue and grey tints on cotton and viscose. It comprises the process of making the new products, the new products themselves, and the material dyed with the said products.

The manufacture consists in coupling diazo-compounds of the benzene series which do not contain nitro-groups with a product of the general formula 1 in which 00 in one case signifies an hydrogen atom and in the other case an hydrogen atom or an SO H-group, then diazotizing the monoazo-dyestuff thus obtained and coupling with certain derivatives of the 2-amino-5- hydroxynaphthalene, i. e. compounds of the general formula wherein R stands for an hydrogen atom or a phenyl or benzyl residue directly bound to the nitrogen atom and free from NH groups. The dyestuffs thus obtained may be converted into new metal derivatives by treatment with agents yielding metals. A similar result is attained by coupling the diazotized monoazo-dyestuff with the 2-amino-5-hydroxynaphthalene in presence of an agent yielding metal. If there is used as the first diazotizing component one which contains a saponifiable acidyl-group the latter may be removed by treating the finished disazo-dyestuff with a saponifying agent.

The new dyestuffs which correspond with the general formula wherein R stands for a residue of a diazotizing component of the benzene series containing no nitro-group, m in one case stands for a hydrogen atom and in the other for a hydrogen atom or an SO H group, and R for hydrogen or; benzyl, methyl, ethyl, phenyl, (methyl) -phenyl, (alkoxy) -phenyl, etc., dye cotton and artificial fibers from regenerated cellulose blue tints which may vary, according to the components selected, from reddish-blue to green-blue. Such dyeings may have a remarkable fastness to light; also the property of many of these products to yield very equal tints on the socalled stripy viscose is of value.

The following examples illustrate the invention, the parts being by weight Example 1 The diaZo-solution produced from 17.3 parts of aniline-Q-sulfonic acid is mixed with sodium acetate until the reaction for mineral acid can no longer be detected, and is then coupled with a neutral solution of 25.3 parts of l-amino-2-methoxynaphthalene-6- sulfonic acid. The monoazo-dyestulf thus formed is dissolved'by addition of sodium carbonate while heating, and is then salted out in the form of its sodium salt by addition of common salt; the sodium salt is then filtered and again dissolved to be mixed at 10 C. with 6.9 parts of sodium nitrite and afterwards with 30 parts of hydrochloric acid of 30 per cent strengths This diazosolution is allowed toflow into a solution alkaline with sodium carbonate of 31.5 parts sulfonic acid. -When coupling is complete the dyestuii corresponding to the formula S0311 is salted out, filtered and dried. It dyes artificial silk from regenerated cellulose equal, clear blue tints. The final coupling may also be carried out in presence of pyridine.

Emample 2 The disazo-dyestufl obtained as described in Example 1 from 17.3 parts of metanilic acid as first component instead of aniline-2- sulfonic acid is dissolved in 500 parts of water; the solution having been made slightly acid with acetic acid is mixed, while boiling, with a solution of copper sulfate of 10 per cent strength until no more copper is taken up by the dyestuii. The whole is then filtered and the solid matter dried. The dyestufi' containing copper thus made dyes in a feebly alkaline bath a blue tint which is considerably more greenish than that of the product which does not contain copper.

For introducing the copper, cuprammonia or some other soluble complex copper compound may be used. This treatment may obviously be conducted in the dye-bath or on the fiber. Among the dyestuiis which are particularly suitable for making such complex metal compounds are those which contain a carboxyl-group or one or more COOH- The procedure is similar with other components. Among compounds whose diazocompound may advantageously be used as first component may be named sulfanilic acid, metanilic acid, toluidine-sulfonic acid (CH zNH zsO H lt lzii or 1:4:2 or 1 2 l), mono-acetyl-l l-phenylenediamine, l-amino-l-acetylamino-b e n z e n e-EZ-sulfonic acid, l-oxalylamino leaminobenzene-Z-sulfonic acid, chloro-aniline-suliionic acid (NH zClzSO H=l:-lz2 or lz lz3 or 1:2:5), dichloro aniline sulfonic acids (N :Cl:Clzso l l lzfzz5:4: or 1:2:5: 6) 2-acetylaminod-chloro-5-aminophenolmethyl ether, Xylidine-sul'fonic acid (CH CH :NH :SO H-=l:3:4:5 or 1:3:lzti), chloro-toluidinesulfonic acid (CH NH Cl: Sad-1 112:53), aniline-Qz lor -3:5- or 2:5-disulfonic acid, toluidine-2z5-disulionic acid (CH :NH :SO I :SO H=l:i: 2 5) at-methyl-2-aminodiphenylsulfoneelsulfonic acid, para-aminosalicylic acid, sulfoaminosalicylic acid (OH: NH COOH: SO H= 1 6 2 a), 3-amino-l-sulfobenzoic acid, l-metl1yl-4-aminodiphenylamine-2-sulfonic acid, and so on. As suitable middle components may be named the methyl, ethyl, propyl, butyl etc. ethers of the l-amino-Q- hydroXynaphthalene, or the 6- or 'T-sulfonic acids of these products. As suitable end components may be named various N-(methyl)- plienyl, N- (dimethyl) -phenyl, N- (methoxy) phenyl, N hydroxyphenyL, N hydroxyphenylcarboxylic acids, N-benzyl-, N-allrylderivatives of 2-ainino-5-hydroxynaphthalene-T-sulionic acid.

The following table shows the shades of some of the combinations of the present ingroups 111 ortho-position to an OH-group. vention 1st component 2nd component 3rd comp n n Shade of dyein I. 1 3-aniline sulphonic acid 1-amin0-2-methoxynaphthalene-G-su1- 2-amino-5-hydroxy-naphtha1ene-7-sulf Reddish-blue fonic acid ionic acid 1 II. Do. Do. 2 plienylamino 5 hydroxynaphthai Blue lenc-7-sulfonie acid III. Monoacetyl-l:4-phenylcne-dia1nine Do. Do. Do. Do. Do. Do. Do.

(Copper compound) IV. 1-amino-bacetylamino-be11zc11e-2- Do. 2-amino-5-hydroxy naphthalene-7- Greenisli-blue sulphonic acid sulphonic acid V. Do. Do. 2-phenylamiuo-5-hydroxynaphthalenc- Do.

7-su1phonic acid VI. Do. l-amino-2-ethoxy-naphthalene-6-sul- Do. Do

ionic acid VII. Aminocrcsol methylcther CH3: 1-arnino-2-methoxyamphthalene-fi-sul- 2-phenylamino -5 hydroxynapht1ia- Blue N 2: CH3= 13M Ionic acid lene-7-sulfonic acid VIII. Do. Do. 2-amino-5-hydroxynaphLhalenc-T-sul- Navy-blue sulfonic acid IX. Toluidine-sulfonic acid CHzuNHz: Do. Do. Rcddislrbluc S 0 13: 114:3 X. Do. Do. 2 phenylamino 5 hydroxynaphtha- Do.

lene-7-sullonic acid XI. Chloro-aniline-sulfonic acid N112: Do. Do. Greenish-blue ClZSO3H=1Z422 XII. Do. Do. 2-amino-5-l1ydroxynaphthalone-7-sul- Blue ionic acid. XIII. Chloro-aniline-sulfonic acid NHzZ Do. Do. Rcddish-blue C1:SO3H=1:2:5 XIV. Do. Do. 2 phenylamino 5 -li vdroxynapl1tha- Blue lene-T-sulphonic acid XV. Chloro'aniline-sulphonic acid N112: Do. Do. Do.

Cl:SO3H=1:4:3 XVI. Do. Do. 2-arnino-5-hydroxynaplithalene-7-sul- Rcddisli-bluc Ionic acid XVII. Z-acetylamino--chloro-5-amino- Do. Do. Green-blue phenol-methylether XVIII. Do. Do. D0. 7 Do.

(Saponified after the coupling) 3rd component Shade of dyeing 2 phenylamino 5 hydroxynaphthaleigH-suiphonic acid Greenish-blue Reddish-blue Do. ionic acid Do. Greenish-blue Reddish-blue 2-amino-5-hydroxynaphthaIene-7-sul- 2 phenylamino 5 hydroxynaphthalerlip-7-sulfonic acid Do. Greenish-bluc Do. Do.

Do. Do.

Do. Do. (Copper compound) 2-amino-5-hydroxynaphthalene-7-su1- Blue ionic acid o. Greenish-blue (Copper compound) 2-phenylamino-5-hydroxynaphthalenc- Do.

7-sulfonic acid Do. Green-blue (Copper compound.) 2-amino-5-hydrox ynaphtha1ene-7-su1- Do.

ionic acid The formula of the dyestuff V. corresponds with the following HN so:

to (EH3 The formula of the dyestuff XVIII corresponds with the following V HQaS- NH,

7 SOaH What I claim is 1. A manufacture of disazo-dyestuifs dyeing cotton and viscose silk blue to greenishblue tints, consisting in coupling a (hamcompound of the benzene series which contains no nitro groups, with a compound of the general formula SOsH o-ona in which as in one case stands for hydrogen and in the other case for SO H or hydrogen, diazotizing the monoazo-dyestuff thus obtained and coupling the diazo-compound in an alkaline medium with a compound of the general formula wherein R stands for an hydrogen atom or a phenyl or benzyl residue directly bound to the nitrogen atom and free from NH groups.

2. A manufacture of disazo-dycstufls dyeing cotton and viscose silk blue to greenishblue tints, consisting in coupling a diazocompound of the benzene series which contalns no nltro groups,

with a compound of the general formula in which a: in one case stands for hydrogen and in the other case for SO H or hydrogen, diazotizing the monoazo-dyestuff thus obtained and coupling the diazo-compound in an alkaline medium with a compound of the general formula HOaS NHR I OH R signifying H or a benzene nucleus directly bound to the nitrogen atom and free from NH groups.

3. A manufacture of disazo-dyestufls dyeing cotton and viscose silk blue to greenishblue tints, consisting in coupling a diazo-compound of the benzene series which contains Tfo'nitro groups, with a compound of the general formula ()-a1ky1 in which 00 in one case stands for hydrogen and in the other case for SO H or hydrogen, diazotizing the monoazo-dyestulf thus obtained and coupling the diazo-compound in an alkaline medium with a compound of the general formula HOaS NHR R signifying H or phenyl.

4;. A manufacture of disazo-dyestuifs dyeing cotton and viscose silk blue to greenishblue tints, consisting in coupling a diazocompound of the benzene series which contains no nitro groups, with a compound of the general formula (1) alkyl 111 which 00 in one case stands for hydrogen and in the other case for SO H or hydrogen, diazotizing the monoazo-dyestuff thus obtained and coupling the diazo-compound in an alkaline medium with a compound of the general formula HOaS NHR R signifying phenyl.

5. As new products of manufacture the disazo-dyestuifs corresponding to the general formula in which R signifies the residue of a sulfonated diazo-compound of the benzene series which contains no nitro-groups, w in one case stands for an hydrogen atom and in the other for an hydrogen atom or a sulfo-group, and R signifying an hydrogen atom or a phenyl residue directly bound to the nitrogen atom and free from NH groups, which products form dark powders, dissolving in water to blue to green-blue solutions, and dyeing cotton and viscose silk similar tints.

7. As new products of manufacture the disazo-dyestuffs corresponding to the general formula in which R signifies the residue of a diazocompound of the benzene series which contains no nitro-groups and possesses an SO H- group in ortho-position to the azo-bridge, m in one case stands for an hydrogen atom and in the other for an hydrogen atom or a sulfo-group, and R signifying an hydrogen atom or phenyl, which products form dark powders, dissolving in water to blue to greenblue solutions, and dyeing cotton and viscose silk similar tints.

8.-As a new product of manufacture the disazo-dyestufi corresponding to the formula which product forms a dark powder which dissolves in water to a green-blue solution, dyeing cotton and viscose silk green-blue tints.

9. As a new product of manufacture the disazo-dyestuff corresponding to the formula which product forms a dark powder which dissolves in water to a green-blue solution, dyeing cotton and viscose silk green-blue tints.

10. As a new product of manufacture the disazo-dyestufl' corresponding to the formula SOaH which product forms a dark powder which dissolves in water to a green-blue solution, dyeing cotton and viscose silk green-blue tints.

In witness whereof I have hereunto signed my name this 16th day of January, 1930.

JOSEPH GYR.

1103s NH-OoHa 

